JPS61134337A - 1-(1'(or 2' or 3')-formylpropoxy)-hexane and perfumery composition containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (formyl group is bonded to 1', 2' or 3' site). USE:Perfumery. It has fresh citrus fragrance accompanied by slight grassy green sense. PREPARATION:The compound of formula I can be prepared by reacting the 1-allyloxyhexane of formula II with CO and H2 in the presence of a rhodium catalyst and a tertiary phosphine at 80-130 deg.C under 20-250atm. The rhodium catalyst is preferably RhH(CO)(PR<1>R<2>R<3>)3, and its amount is preferably 0.001-1.0mol% based on the compound of formula II. The tertiary phosphine is effective to suppress the formation of a high-boiling by-product, and is preferably the one expressed by the formula PR<1>R<2>R<3>. The amount is 1-10,000mol per 1mol of the rhodium catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel aromatic compound, more specifically, to a compound of the following formula (1
) (In the formula, the formyl group is bonded to the 1', 2' or 3' position.) ]-Hexane and a fragrance composition containing the same.

[Conventional technology]

Hitherto, many useful fragrance compounds have been known including KFi among saturated or unsaturated aldehydes (M, Bt@l@
ms, H:, J, Wobb@n+J, Hlydel j
P@rfum*r & Flavorist, 5 (
1'h6) -1 (1980); Hito, F. Morri
m*P*rfum@r & Flavorl st
, 6(mx), t(19sx)]. It is also known that allyloxylated compounds are useful as perfuming ingredients (US Pat. No. 4,443,633).

[Problem that the invention seeks to solve]

However, the aromas of compounds are generally completely different due to slight structural differences, so it is extremely important to synthesize various compounds and study their aromas in order to obtain new fragrances.

[Means for solving problems]

The present inventor synthesized an allyloxy compound and conducted various studies on the aromatic properties of the resulting okino reaction product. As a result, the following formula (1) obtained by reacting n-hequinanol and allyl bromide was found. The okino reaction product of 1-allyloxyhexane represented by the formula % (1), that is, the compound of (1), has a bright citrus-like aroma with a slight grass-like green feeling, They discovered that it is useful as a fragrance and completed the present invention.

That is, the present invention provides 1-[1' (or 2' or 3')-formyl]-hexane represented by the (summer) formula and a fragrance composition containing the same.

The compound (f) of the present invention is produced from K by reacting the compound (R) with carbon monoxide and hydrogen in the presence of a rhodium catalyst and a tertiary phosphine.

As a rhodium catalyst, Rh1l[(Co)(PR'R
“R”)s.

RhCt(Co)(PR”R”R”)talsohR
hC1(PR"R"R")s (in the formula Hl, H
1 and R1 are the same or different, and preferably an alkyl group, a cycloalkyl group, or an aryl group (where 1 represents an alkyl group having 1 to 6 carbon atoms or an aryl group substituted with an alkoxy group), and is particularly a catalytically active species. Rha (co)
(pm"g"u')s Kaliket t, i. From the viewpoint of catalyst weighing reactivity and economic efficiency, 0.0 for compound (1) K
A range of 0.01 to 1.0% is suitable.

Tertiary phosphine is used for the purpose of suppressing the production of high boiling point substances and is represented by the general formula 4 PR'R"R'C (where R1, B* and R1 have the same meanings as above). is preferable, and it is preferable to use 1 to 10,000 times the mole of the rhodium catalyst.

The reaction temperature is 0 to 170°C, preferably 80 to 130°C;
The reaction pressure is 20 to 250 atmospheres; the mixing ratio of carbon oxide and hydrogen (carbon oxide/hydrogen) is suitably 0.5 to 2.0 in terms of partial pressure ratio.

This reaction can be carried out in the absence or presence of a solvent. However, in view of post-processing effort, it is preferable to use no solvent.Tt1, for example, ttf hexane, benzene, toluene, ether, chloroform, etc. can be used as the reaction solvent.

The mixture obtained by the reaction can be purified by distillation under reduced pressure and can also be separated from the catalyst.

It was confirmed by the following method that the mixture obtained as described above was composed of compound (1).

It is known that the lozocum compound used as a catalyst for the oxo reaction generally catalyzes the isomerization reaction of allyloxy compounds to vinyl ethers. Therefore, when compound (1) is subjected to an oxo reaction, the reaction is carried out in three types (Ia, Ia,
Ib, Ia) is expected to be produced.

The margin below + + The product purified by vacuum distillation (8LO~87.0℃/4■if) was added to a cavity 2 column [Hyuret・
Paracard's Carbo Wax ((arbovax))
When subjected to gas chromatograph graph analysis using a 20 Mm column length (50 m), three peaks were observed as shown in Example IK. Furthermore, according to 'BNMRK, there are three types of products (1
The structure was determined to be a mixture of isomers of m, 1b, and Ie), that is, compound (1). These three types of isomers all have similar scents and do not necessarily need to be isolated for use as fragrances.

〔Effect of the invention〕

The compound (t) Fi of the present invention has a fragrance with a fresh citrus-like aroma and a slightly greenish feel, and also has a strong residual fragrance, so it can be used, for example, in high-grade fragrance compositions, perfumes, etc. It can be widely used in soaps, shampoos, hair rinses, detergents, cosmetics, ssollets, fragrances, and other items that require fragrance.

〔Example〕

Next, the present invention will be explained with reference to reference examples and examples.

Reference Example 1 Synthesis of 1-aryaoxyhexene (summer): Tetra-n-butylammonium bisulfate (84,89f- 0,25mot), n-heki? /-le (102,18f, 1m@li, a-hexane (20
4,36F), 50% by weight aqueous sodium hydroxide solution (8
00f, 10 motNaOH), this is KW111! allyl bromide 241. while stirring.
96f, 2m@t) should be dripped over an hour. This mixture was stirred at room temperature for 3 hours. Hexane (5
00-) and water (1 t) were added to separate the layers, and the hequinane layer was washed three times with water (1 t). The hequinane layer was dried over anhydrous am magnesium, separated by F, and then subjected to fractional distillation to obtain the above compound 122.53 f (86.1% yield). This one is green like watercress and has a pezotaple note scent.
- It was a colorless and transparent liquid.

Boiling point: se, o~59.5℃/16 mmHf Elemental analysis (as C*HtsO) tt Calculation fullejQ: c,? 6.00 :a
・* 12.75 actual measurement value ~: c, 7 & 81: is 1
λ82IR (liquid film tca-1): 3100(νCH("Cto,"cHt)]2940
, 2870(u,,) 1650(ν(=(>1120(ν.-〇) 990 ,920 (δ.H(-C1i=out-of-plane bending angle of CIIt)]')l-NMR(CD C1, solvent ,'r
Ms internal standard, δ): 6.21-5.60 (-CHl
-CH=CH2-11T1m)5.36~4.95 (
-CH=C%, 2HIm) 3.94 to 3.83 (-0
-CHI-CM-=, 2H1m) 3.48-3.26
(-CH, -CHl-0-, 21, m) 1.76-1.
25 (Cll5-(C11i2)4-CH2-+ 8
11 lc amp lax@d m)0.94~0.
76 (CHI-CHl--3H-!!I)MS (
Relative Intensity) The results of a pneumatic gas mass measurement using CARBOWAX 20M (Hieret IQ Tucard, column length 50 m) are shown below.

142CM, 01), 113 (23), 8
5 (32), 71 (28), 58 (100), 57
(4G), 56(26).

55 (30), 43 (94), 41 (79)
Example 1 1- Synthesis of 1-(1' (nu is 2' or 3')-phorzolzolo?xy)-hexane (1) = 1-allyloxyhexane (1) (40t.

0,281 mot) -RhH(COXPPhi)s
(0,258 cent f, 2.81
mot) into a low autoclave. After replacing the air in the autoclave with nitrogen, c.

The autoclave was then heated to 110° C. and stirred. If the durzo pressure becomes 20 atm or less, the equal partial pressure C
O and H are pressurized to 100 atm. The reaction ends when gas absorption stops. This opening took about 6.5 hours. After cooling the autoclave to room temperature and returning it to normal pressure, the contents were taken out and fractionated to form the above compound 42.
68 tons (yield: 88.2%) were obtained. - [In this case, a small amount of 0X-(1'-7"lopenyloxy)-hexane was produced as a by-product.] This is a colorless and transparent liquid with a fresh citrus-like aroma and a slight grass-like green scent. Met.

Boiling point: 82.0-87.0℃ 74 mm Hf
Elemental analysis (as CxeHteOt) Calculated value (g): Ce69.72:l[,11,70 Actual value ring: C,69,41:H,11,60IRC liquid metal,
Communication-1): 2940.2870 (νC□) 2725 (νcH (CHO)] 1725C C yo. (CHO) ] 1110 (C, o (c-o-c)) 'H-NMR (CDC4 solvent, TMB Internal standard, δ):
eompl@z@d m ) CHO 2,74-2.34 (-CIO, CHCH3, and-
CHICHt C[0-m)2.07~0.77 (
a amp l@x* d m)M5 (Relative intensity) This compound has three types of isomers derived from differences in the bonding position of the formyl group.

The results of gas mass measurement of this compound using a capillary column (same as in Reference Example 1) are shown below.

Peak 1 (15%): 149 (0,3), 14
3 (20), 86 (4), 85 (55), 59 (76
), 57(25), 55(9), 43(100),
42 (4), 41 Beak 2 (33%): 172 (
M”, 3.1).

85 (84), 71 (22), 70 (27)
, 57(32).

56 (22), 55 (30), 43 (100), 42 (
25).

Beak 3 (52%): 149 (0,2), 113 (6
3), 85 (40), 84 (37), 5a (a, o),
82 (60), 71 (77), 56 (37), 43 (1
00).

Regarding Sc-ri 1 and G-3, m/・190 ((M+NH4)) is observed in the chemical ionization mass spectrum using ammonia as the reaction gas, so these peaks are also determined by the molecular weight. It is found to be the aldehyde form of 172.

Example 2 Linden starch foursome type (Llnd@nBlosso
m Types) Fragrance: Hydroxy Citronella K
150 parts by weight Linaloo h
150α-ionone
ZG.

Phenylethyl Alcohol 100 Pencil Salicylate 30 Hexyl Salicylic) 20 Garnosum Oy) h 2 Oydanotasi
5 coumarin
5 Zopropylene Glycol 3
38 By adding 10 parts by weight of the compound produced in Example 1 to 1,000 parts by weight of the linden protusumtide fragrance described above, a more floral and fresh linden protusum type fragrance was obtained.

that's all

Claims (2)

[Claims] (1) 1 represented by the following formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, the formyl group is bonded to the 1st, 2nd, or 3rd position.) -[1 (or 2 or 3)-formylpropoxy]-hexane. (2) The following formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, the formyl group is bonded to the 1', 2', or 3' position) A fragrance composition comprising the following 1-[1' (or 2' or 3')-formylpropoxy]-hexane.